Short-Term Flow Induced Crystallization in Isotactic Polypropylene: How Short Is Short?

Abstract

The so-called “short-term flow” protocol is widely applied in experimental flow-induced crystallization studies on polymers in order to separate the nucleation and subsequent growth processes [Liedauer et al. Int. Polym. Proc. 1993, 8, 236–244]. The basis of this protocol is the assumption that structure development during flow can be minimized and the rheological behavior, i.e., the viscosity, does not change noticeably. In this work we explore the validity of this assumption for short but strong flows and reveal the structure formation during the early stages of crystallization. Viscosity and structure evolution of an isotactic polypropylene (iPP, Mw ≈ 365 kg/mol and Mw/Mn = 5.4) melt at 145 °C are measured during the short-flow period (0.2–0.25 s) using the combination of a slit rheometer and fast X-ray scattering measurements. For high enough (apparent) shear rates (≥240 s–1) a viscosity rise during flow is observed; i.e., the condition for “short-term flow” is not satisfied. With a time delay with respect to the viscosity rise, the development of shish is observed at a position halfway the length of slit, along the flow direction, by means of ultrafast time-resolved SAXS measurements. Depending on the shear rate, these shish are detected during (shear rates ≥ 400 s–1) or after flow (240 s–1 ≤ shear rates < 400 s–1). For even lower shear rates of 160 and 80 s–1, the viscosity does not change significantly, and instead of shish, oriented row nuclei (X-ray undetectable) are generated. These two shear conditions qualify as short-term flow. A full understanding of the coupled flow and crystallization phenomena requires that the transient and nonhomogeneous behaviors, both in flow and in flow gradient direction, have to be taken into account. This can only be done by a full numerical model, and therefore, the results presented in this paper also provide a valuable data set for future numerical studies.